Stabilized hydrocarbon



Patented Feb. 3, 1942 STABILIZED HYDBOGARBON William B. James andEverett W. Fuller, Woodbury, N. 1., assignor to Socony-Vacunm OilCompany, Incorporated, New York, N.-Y., a corporation of New York NoDrawing. Application March 2, 1940, Serial No. 321,922

2 Claims.

Refined petroleum oils generally tend to deteriorate in service and instorage, due to the effects of oxidation and allied causes to formacidic and/or sludge-like materials which are detrimental to thepurposes for which the oils are intended. Acids attack metal surfaces intransformers, turbines, and engines, while sludges precipitate out,clogging passages and tubes to reduce the flow of oil to points where itis needed, and settle on cooling surfaces to reduce the heat transfercapabilities thereof.

This invention has for its object the provision of a novel class ofinhibitive compounds possessed of rather uniform inhibitive capabilitiesover a rather wide field of petroleum derivatives of high boiling point,ranging from lubricating oils of low viscosity to waxes, and effectiveregardless of degree or kind of treatment to which the oil to beinhibited has been subjected.

This invention is based upon the discovery that products resulting fromthe condensation of nitro-aromatic compounds with other'materials,

as naphthylamines, and other organic amino compounds have valuableinhibitive properties.

This invention, from the inhibitive standpoint, is based upon thediscovery that novel inhibitive capabilities are possessed, as describedabove, by products resulting from the condensation of nitro-aromatics,as for example, sym-tri-nitro benzene, (1,3,5, trinitrobenzene), withnaphthylamines, or other amino compounds. Such products for example,those prepared from naphthylamines, are cheap, easy to prepare, stable,and possess'a breadth, consistency and extent of effectiveness quitediilerent from the related naphthylamines, some members of which groupare stabilizers of rather erratic capabilities.

The condensation products referred to may be produced from the indicatedstarting materials by the method of synthesis set forth by J. J.Sudburough, (J. Chem. Soc. 79, 522 (1901)) and subsequently,particularly (J. Chem. Soc. 83, 1 334 (1903) and 97, 7'73 (1910)). Themethod generally is as follows:

.A benzene solution of 1,3,5 trinitrobenzene was added to a benzenesolution of the naphthylamine and after standing a short time at roomtemperature the condensation product separated. It

was, purified by recrystallization from alcohol.

With most of the naphthylamines the reactants 50 secs., at 100 F.

were used in.equa1 molecular ratios but with N- phenyl alphanaphthylamine a better yield is obtained when two moles oftrinitrobenzene are used to one mole of the naphthylamine. The productsobtained were reddish crystals with definite melting points quitediiferent from those of the original amines. For example, the followingcompounds have been prepared from 1,3,5-

trinitrobenzene and the naphthylamine noted below:

Similar products may be obtained by condensing other trinitro aromaticcompounds, such as trinitrotoluene, trinitrocresol, trinitroresorcinoland trlnitroanisole, with naphthylamines or other amino compounds.

The products so produced are capable stabilizers for wide field ofpetroleum derivatives. They are effective in oils which have been highlyrefined by heavy treatments with sulphuric acid. They are effective inoils which have been moderately refined with acid. They are effective insolvent refined lubricating oils, and they are capable of preventingdeterioration of wax by acid formation and similar oxidation reactions.

As with any product used for an inhibitor, oil solubility of theinhibitor is of importance. Only a few of these products have oil slubility so restricted as to hamper their usefulness, and apparentlythen only with a few oils.

The stabilizing effect of these materialsin various petroleum oils isshown by the following by neutralization, washing and clay percolation.

It had a specific gravity of 0.8'71, a flash point of 310 F., and aSaybolt Universal viscosity of 69 This type of oil tends to form acidicproducts on oxidation and it was tested by heating samples to 120 C. andbubbling oxygen through for 70 hrs. The acids thus formed were thendetermined by titrating with alcoholic v ifurfural, dewaxed andfiltered.

All of these products show an appreciableeifeet in stabilizing this oil.C. Oils refined by means of solents.A distillate from a Rodessacrude wasrefined with The finished stock had a specific gravity of 0.856, a flashpoint of 420 F. and a Saybolt Universal viscosity of 151 sec. at 100 F.

This oil was tested by the same method as used just above for. oilsmoderately refined by means of sulfuric acid. The results were asfollows:

TABLE III I Oils refined by means of solvents Percent Time, Lov. Sludge,

cone. hrs. N color mg./25 cc.

Oil alone 0.00 92 0. 91 9 33 165 20. 3 320 251 1,3,5 trlnitrobenzene andbeta-naphthylamine 164 51 6 356 30. 0 605 382 1,3,5 trinitrohenzene andbutlvllu-l alpha naphthy inc 164 01 1 350 01 1 39 1,3,5trinitrobenzeneand gihenyl alpha naph hyiamine 05 164 02 1 356 01 1 5 1,3 5trlnitrobennene and diethyl alpha-naphthylamlne 05 164 61 7 I 2,4,6trinltrotoluene and beta-11a hth lamina 05 164 21 5 2,4,0 trini oto noneand henyl alpha naph thyiamine 05 164 01 7 356 01 1 21 2,4,6trinitro-m-c'resoi and lrliheuyl alphanapht ylamine 05 164 01 1 356 01 14 potash. Results for the oil alone and with the 5 addition of thestabilizers herein disclosed are given below in terms of N. N. value(mg. of KOH requiredto neutralize the acids in 1 gram of oil) TABLE IOils highly refined by means of sulfuric acid P z N. N 801? value 15 Oilalone v I 0.11) 25.0 1,3,5 trinitrobenzeno and beta-na hthylamine.-. .051 7.0 1,3,g1gig1itrobenzene and butylpha-naphthyl- .05 .23

a 1,32,: grlirrli igobenzene and phenyl-alpha-naph- .05 0'0 2,4,6trinitrotoluene and beta-naphthylamine 05 3. 8 2,4,ggi1itrotoluene andphenyl-alpha-naphthyl- .05 .06

8 2,4,6 trinitro-m-cresol and phenyl-alpha-naph- .06 0.0 thylamine.

. It is noted that the products effectively stabilize this oil. B. Oilsmoderately refined by means of sulfuric acid.--A mixed Mid-Continent andCoastal distillate had been refined by treatment with 70 9 lbs. of 98%sulfuric acid per bbl., neutralized, washed and percolated through clay.It had a specific gravity of 0.879, afiash point of 385 F.

and a Saybolt Universal viscosity of 152 secs. at 100 F. It is an oilsuitable for usein turbines. It was tested as follows:

25 cc samples of the oil were heated to 200 F. with 5 liters of air perhour bubbling through them. 24 inches of #18 gauge copper wire and 1 40gram of iron granules were added to each saniple. Also 2 cc. ofdistilled water were added each day. The samples were examined foracidity, color and sludge after varying periods of time.

' TABLE II Oils moderately refined by means of sulfuricacld I PrntTim,Lo.-8id,

803%. hrs: N'N' colgr 32525.

011 alone"; 000 72 0.14 c as 240 2.5 110 240 330 no 400 1,232 1,3,5trinitrobenzene and beta-naphthylamine .05 154 .17 12 q 356" 3.0 72 1111,3,5 trinitroben'zene and butyl-alpha-naphthylamine .05 164 .01 2

s50 .05 ,5 11 1,3,5 tnnitrobenzene and phenyl alpha -napl1thylamine .05164 .01 "3 35c .02 5 7 1,3,5 trlnitrobenzene anddiethyl-alphanaphthylamlne .05 164 -01 2 355 2.2 50 30v 2,4,6trinitrotoluene and beta .naphthylamine .05 154 .4 0 355 1.7 51 8? 2,4,6trinitrotoluene and phenyl alpha naphthylamine .05. 164 0.0 a

355 0.9 27 s 2,4,6 trinitro-m-cres0l and phenyl alpha- Y naphthylamine.05 164 1.7 32

All of these products show an appreciable effeet in stabilizing oil.

1) A further example of the stabilizing action of these compounds isshown by the following test results. Motor oils, especially thoserefined by certain solvent extraction methods, tend'to oxidize whensubmitted to high temperatures and to form products that are corrosiveto metal bearings. This corrosive action may be quite severe withcertain bearings, such as those made or cadmium-silver alloys, and maycause their failure within a comparatively short time. The iollowingtest was used to determine the corrosive action of a motor oil on anautomobile connecting rod bearing. 5

The oil used consisted of Pennsylvania neutral and residuum stocksseparately refined by means 01' "chlorex and blended to give an S. A. E.20 motor oil with a specific gravity of 0.872, a flash point of 435 F.and a Saybolt Universal viscosity of 318 sec. at F. The oil was testedby adding a sectional a bearing. containing a cadmium-silver alloysurface and weighing about 6.0 grams, and heating it to C. for 22 hourswhile a stream of air was bubbled against the surface" of thebearing.The loss in weight of the bearing during this treatment measures theamount of corrosion that has taken place. A sample of the oil containinga stabilizer was run at the same time as a sample of the straight oil.The loss in weight or the section 0! the results were obtained:

TABLE IV solvent refined motor oil Mg. loss in weight Percent oono.

Inhibited Unlnhibited amine .o '1,3,5 trinitrobenzene and 1,3,5trinitrobehzene and alpha-naphthylamine 05 ii 1,3,6 trinitrobenzene andbeta-nephthylamine 1 1,3,5 trinitrobenzcne and butyl-elpha-nephthylpheuyl-eIpha-naphthylamine 1,3,5 trinitrobenzene and diethyl-elphs-naplith yiamino 2,4,6 trinitrotoluene and betauephthylamine2,4,6 trlnitrotoluene and beta naphthylamlne 2,4,6 trinitrotoluene andphenyl-elpha-naphi-hyl-nmine. 2,44; triniti'ooluenfitgnii any -a a-nsp yuinea? .05 27 These compounds are also efiective stabilizers of perefiinwax, as may be seen from the following:

E. A refined paramn wax. of 126 F. melting point was tested by heatingto 120 C. for '70 hours with oxygen bubbling through it. 80

TABLE V Parafin was:

conc. value We: alone 35. 6 l, 3, '5 'lrinitrobenzene andbutyl-elpha-naph thylnmina 05 Q 0 2, 4, 6 Trinltrotoluene andpheuyl-alpha-naph thylamine 2, 4, 6 Trinitro-m-cresol andphenyl-alpha-naphthy 05 0. 0

Percent N. N. 35

In general these compounds when used for in hibitio'n will befound to beeffective in concentrations of from about .01 to about 0.10 weightpercent of the oil to which they are added, and preferably may be usedin concentrations of about 0.05 to about 0.10 weight percent. For mostof the compounds the solubility in oil will be suilicient to attain suchconcentrations, or if not, at least great enough to obtain a usefulinhibiting effect. when the term oil-soluble" is used, it indicates asufiioient solubility for the purposes of the invention,

Since the capability of these inhibitors ranges over the field oflubricating oils and waxes, and is not restricted by prior treatment ofthe lubricating oil, that field is defined herein by the term highboiling refined petroleum fraction."

We cleim:

1. A high boiling petroleum product stabilized against formation ofacidic and sludge products of oxidation by the addition thereto of asmall amount, sumcient only to inhibit oxidation, of the oil solublecondensetionreaotion product formed by reacting a. tri nitrated memberof the group consisting of benzene, toluene, cresol, resorcinal,anisole, with a member of the group consisting of nap-hthylemine andsubstituted naphthylamines.

2. A high boiling petroleum product stabilized against formation ofacidic and sludge products of oxidation by the addition thereto of asmall amount, from about 0.05 to 0.10 weight per cent of the oil solublecondensation reaction product formed by reacting a tri-nitrated memberof the group consisting of benzene. toluene, cresol, resorcinol,anisole, with a member of the group consisting of naphthylamine andsubstituted naphthylamines.

WILLIAM H. JAMES.

EVERETT W. FULLER.

